Journal of Membrane Science 272 (2006) 5057

Casting Naonsulfonated organosilica nano-composite membranes used in direct methanol fuel cells
Chennan Li a,b , Gongquan Sun a, , Suzhen Ren a , Jin Liu a,c , Qi Wang a,b , Zhimou Wu a , Hai Sun a , Wei Jin a,b
a

Direct Alcohol Fuel Cells Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China b Graduate School of the Chinese Academy of Sciences, Beijing 100039, China c Department of Material Science and Engineering, Anhui Institute of Architectural and Industry, Hefei 230022, China Received 21 March 2005; received in revised form 15 July 2005; accepted 17 July 2005 Available online 6 September 2005

Abstract Solgel derived sulfonated diphenyldimethoxysilane (sDDS) with hydrophilic SO3 H functional groups were used as the additive to reduce the methanol permeability of Naon. The Naon-sDDS (N-sDDS) nano-composite membranes were prepared by mixing Naon-dimethyl formamide (DMF) solutions with sDDS sol and casting to membranes. Swelling weight (SW) test and SEM characterization show the physical properties of the composite membranes and FT-IR analysis reveals the incorporation of the sDDS monomer within the composite membranes. The composite membranes methanol permeabilities are tested by gas chromatography according to the amount of the sulfonated silane. The cell performances of the N-sDDS membrane are evaluated and compared with the unsulfonated DDS composite membrane and Naon 117. It was found that, compared with the Naon 117 membrane, the nano-composite membrane with the thickness of 125 m has a lower methanol permeability and better single cell performance than the unsulfonated DDS composite membrane. 2005 Elsevier B.V. All rights reserved.
Keywords: Naon; Nano-composite membrane; Proton conductivity; Methanol permeability; Direct methanol fuel cells (DMFCs)

1. Introduction Peruorosulfonic acid membranes such as Naon are widely used in direct methanol fuel cells (DMFCs), which are promising candidates for the application of portable power sources. However, high methanol permeation through Naon membranes not only latten away fuel but also reduce cell performances [1,2]. Therefore, a breakthrough is needed to reduce the methanol crossover and, consequently, improve the performance of the methanol-fed devices. Amongst the Naon based composite membranes seem a promising way and various attempts have been made such as modication of Naon with Pd [3], Pd alloy [4], polyvinyl alcohol [5], polypyrrole [6], zeolite [7], silica and molybdophosphoric
Corresponding author. Tel.: +86 411 84379063; fax: +86 411 84379063. E-mail addresses: chennanli@hotmail.com (C. Li), gqsun@dicp.ac.cn (G. Sun). 0376-7388/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2005.07.032

acid [8], montmorillonite [9] and polyfurfuryl alcohol [10], or recast hybrid membrane from Naon solution with some materials such as platinum [11], titania [12], heteropolyacid [13,14], silica [15] and phenethyltrimethoxysilane [16]. Up to now, conventional modied Naon membranes cannot meet the requirements for practical DMFC applications. Thus, the research on low methanol permeation Naon based composite membranes still remains active. The incorporation of hygroscopic particles such as silica within Naon membranes in previous studies aims at improving the operation temperature thus enhance the kinetics of the methanol oxidation. Whereas in this paper, we report a novel approach to the Naon/sulfonated organosilica composite membrane. The hybrid membranes were obtained by recast Naon solution with sulfonated diphenyldimethoxysilane (sDDS), which has proton conductive SO3 H functional groups through sulfonating DDS monomer. The sDDS act as an additive to improve the proton conductivity compared

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with purely adding DDS to the membrane and the unreacted phenyl groups acted as the hydrophobic groups to reduce the methanol permeation. Preliminary results of water uptake, proton conductivity, methanol permeability and cell performances of the Naon/sDDS (N-sDDS) composite membranes are reported.

2. Experimental 2.1. Preparation of composite membranes The preparation protocol of N-sDDS composite membranes is shown in Fig. 1. The preparation protocol of N-sDDS composite membranes is shown in Fig. 1. Diphenyldimethoxysilane (DDS) monomer was kindly provided by Hu Bei Huabang Chemical Co. Ltd., China. Sulfonated DDS was obtained by sulfonating DDS with chlorosulfonic acid dropwise adding into DDS under rigorous stirring at ice water mixture. The mixed solution was stirred at 50 C overnight to complete the sulfonation of phenyl groups. The solution of the sulfonated DDS was DMSO-d6 when conducting H-NMR experiments. Afterwards 5 g of the reacted solution were measured and added into 200 ml dimethyl formamide (DMF) with stirring for 23 h. After that, measured amount of deionized (D.I.) water was added into the solution to give a molar ratio of sDDS:H2 O = 1:5. Hydrolysis of sDDS was carried out under self-acid-catalysis of the sulfonic groups under stirring for 1 day. Thus the nal sulfonated silica sol was obtained. The N-sDDS composite membranes were prepared from 5 wt.% Naon solution (DuPont, equivalent weight (EW) = 1100 g mol1 SO3 H) according to the following processes: (1) evaporation of the Naon solution under 60 C for 12 h till the Naon solution became solid resin, and (2) redissolve the Naon resin with a desired volume of DMF

(the volume ratio of DMF/Naon is approximately 1525). (3) Measured amounts of silica sol and Naon DMF solution were mixed and under ultrasonicate processing for 15 min to ensure complete mixing. (4) The mixed solution was casted into glass model and preheated to 80 C till most of the solution was evaporated. The thickness of the composite membranes could be controlled by the amount of dry Naon resin. (5) The solid Naon membrane obtained was then placed in a vacuum oven at 145 C to remove the last traces of the high boiling solvent. The nal annealing process lasts for at least 3 h. Purely recast Naon membrane was also made by the procedures mentioned above as a comparison with the N-sDDS composite membranes. A series of composite membranes which have 5, 10, 15, 20, 25 sDDS by weight compared with the dry Naon resin were denoted as the 5NsDDS, 10N-sDDS, 15N-sDDS, 20N-sDDS and 25N-sDDS respectively. In this paper, the bare recast membrane and the series composite membranes used to measure methanol permeability are 75 m and the composite membranes used for evaluating the cell performances are 125 m average in order to sustain 0.2 MPa oxygen pressure in the cathode. 2.2. Conductivity measurement The proton conductivity of samples in the traverse direction was measured by the two electrode AC method and the apparatus is self-designed by our laboratory. The measurements were carried out on the potentiostat/galvanostat (EG&G Model 273A) and Lock-in (EG&G Model 5210). A high frequency up to 105 Hz is used in order to separate membrane resistance from interfacial capacitance and the software Powersuite was used to collect data and plot gures. All the membrane samples were in their protonated state and immersed in room temperature water overnight prior to measurement. The circumstance of the measurement is 100% humidied. The proton conductivity was calculated from the impedance data, using the relation: = L RS (1)

where L and S are the thickness and area of the membrane, respectively, and R was derived from the low intersect of the high frequency semicircle on a complex impedance plane with the Re(z) axis. 2.3. Membrane swelling weight (SW) and equivalent weight (EW) measurement The membranes were dried in a vacuum oven at 100 C for 24 h, weighed, soaked in deionized water overnight at room temperature, blotted dry with absorbent paper to remove any surface moisture, and reweighed. Liquid uptake was calculated from
Fig. 1. Preparation scheme of N-sDDS composite membrane.

SW =

Gw Gd 100% Gd

(2)

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C. Li et al. / Journal of Membrane Science 272 (2006) 5057

Here, Gw is the weight of the wet membranes and Gd the weight of the dry membranes. The dried membranes were dipped in a 1 M NaCl solution at 80 C overnight to exchange Na+ ions with H+ . Then removed the membrane from solution and titrated the solution to end point with 0.1 M NaOH solution to determine the quantity of exchanged H+ ions (Phenolphthalein as the indicator). The EW was calculated using the dry weight of the polymer and the quantity of exchanged protons. 2.4. FT-IR spectroscopy and scanning electron microscopy (SEM) The spectra were collected on a Nicolet Avatar-370 equipped with a DTGS detector and a ZnSe crystal (45 angle) as attenuated total reection accessory. A spectrum, collected as the average of 64 scans with a resolution of 4 cm1 , was recorded from 4000 to 400 cm1 for the transmission mode, while 4000650 cm1 for the ATR. All spectra were collected with Omnic 6.1a. The pressure was equal in all ATR measurements to avoid the difference brought by the pressure and penetrating depth. A small amount of sulfonated silica sol was dried at 90 C overnight, ground and compressed into KBr-based wafers for IR analysis. The N-sDDS composite membrane were examined with a scanning electron microscope operated at 1020 kV (SEM, Philips Cambridge S360). 2.5. Membraneelectrode assembly (MEA) The electrodes for single-cell test in DMFCs consisted of gas diffusion and catalyst layers, and the details of the electrode preparation are available elsewhere [17]. The anode catalyst was a commercial PtRu/C (20 wt.% Pt, 10 wt.% Ru, Johnson Matthey) while the cathode catalyst was the carbon supported platinum (Johnson Matthey, Pt 20 wt.%). The loadings of Johnson Matthey PtRu at the anode and Johnson Matthey Pt at the cathode were 2 and 1 mg cm2 in our study, respectively. The MEA was prepared by sandwiching the membrane between two pieces of gas diffusion electrodes, and then hot-pressed at 135 C for 90 s. For comparison, MEAs with bare recast Naon membrane, N-sDDS composite membranes and N-DDS composite membrane were prepared in the same way. The geometrical area of the electrodes was 4.0 cm2 . 2.6. Single cell performance testing Single cell performance was tested at different temperatures with an in-house electrochemical test station and a Fuel Cell Test System (Arbin Instrument Corporation). To ensure that the electrolyte in the membrane and electrode is moist enough to have high ionic conductivity, it is necessary to activate the MEA before the measurement of polarization curves. In our experiment, the cell was conditioned with methanol solution at 60 C overnight prior to the test.

2.7. Methanol permeability and limiting methanol permeation current density The methanol permeability of the membranes was determined by two methods, the rst one is using a glass diffusion cell [9,18]. This cell consisted of two reservoirs and separated by a vertical membrane. One compartment of the cell (VA = 50 ml) was lled with a solution of methanol (1 M) and 1-butanol (40 g/l) in D.I. water. The other (VB = 20 ml) was lled with a 1-butanol (40 g/l) solution in D.I. water. The membrane (area 2 cm2 ) was clamped between the two reservoirs which were both stirred during the experiments. Prior to the test, the membranes were equilibrated in D.I. water for at least 12 h. The increase in concentration of methanol in the B reservoir was measured across time using gas chromatography. In the gas chromatography measurements, 3 l samples were analyzed using a Shimadzu GC14B gas chromatograph. In the permeation tests, the temperature was controlled using a thermostatic water bath. A ux of methanol penetrated across the membrane as a result of the concentration difference between the two compartments. The value of CB was measured several times during the experiments, and the permeability was calculated from the gradient of the straight lines obtained from plots of the data. The second method in our study to measure the methanol crossover was voltammetric method [19], which is set up as described in single cell performance testing except that inert, highly puried N2 instead of O2 was fed into the cathode. Limiting methanol permeation currents through the membrane were measured using Galvanostat Model 273A Electrochemical Interface. Methanol solution was fed to the anode side of the MEA while the cathode side was kept in an inert humidied N2 . By applying a potential from 0 to 0.9 V on the cathode side, the limiting methanol permeation current was obtained by measuring the transport-controlled limiting current of the methanol electro-oxidation process at the Pt/membrane interface. The anode side, where hydrogen evolution took place, served as the counter electrode and as the dynamic hydrogen reference electrode (DHE).

3. Results and discussion 3.1. Proton conductivity The proton conductivity of the composite membrane is shown in Table 1, for comparison, the proton conductivity of the Naon 117 membrane is also shown. It can be noticed that the proton conductivity of the NsDDS is higher than the N-DDS membrane if the same amount of silica is added, which means the sulfonation of the DDS has some function for the composite membrane. Maybe that is because DDS is hydrophobic, some small DDS particles might be embedded in the channels between two clusters, which are less hydrophilic than clusters, but not the clusters.

C. Li et al. / Journal of Membrane Science 272 (2006) 5057 Table 1 Comparison of proton conductivity of a serious of N-sDDS composite membranes, 5N-DDS composite membranes and Naon 117 membrane at room temperature Thickness ( m) 0N-sDDS 5N-sDDS 10N-sDDS 15N-sDDS 20N-sDDS 25N-sDDS Naon 117 5N-DDS 125135 125135 125135 125135 125135 125135 175 125135 Proton conductivity (102 S cm1 ) 2.00 1.57 1.00 0.91 0.879 0.785 2.20 0.40

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This might dramatically effect the proton conductivities of the composite membranes. But the proton conductivity of composite membrane decreased compared with commercial Naon membranes. This is partly because (1) the relative low conductivity of organosilica [20], (2) the slightly tortuous path through the membrane which is caused by the embedding of the organosilica into the hydrophilic clusters [21], (3) and the hydrophobic phenyl groups of the organosilica which change the distribution of the hydrophilic/hydrophobic phases therefore reduce the water content of the membrane [22]. It was also found from Table 1 that the more hybrids the composite contains, the less the proton conductivity it has. This can be explained by the derivative equations of Maxwell in Ref. [21] used in the composite membranes lled with a periodic array of spheres [21] = 2 + 2(1 ) 2 + + (1 ) (3)

Fig. 2. Liquid uptake of membranes at room temperature.

Here the letter demonstrates the ration of the effective H+ diffusion in the composite membranes versus H+ effective diffusion in the Naon phase, and is the ration of H+ diffusion through the sDDS sphere relative to diffusion through the polymer. Therefore the more the (the percentage of the hybrids of the composite membrane) is, the smaller the gains. That means the proton conductivities decrease with the increasing percentage of the sDDS in the composite membranes. Though the proton conductivity decreases, the composite membrane can be fabricated thinner than the Naon 117. And with the changing of the thickness of the composite membrane, the resistance of the composite membranes in the traverse direction can be equal to Naon 117. In this test, though its proton conductivity is a little lower, the 125 m 5N-sDDS composite has the same resistance with Naifon 117 and was chosen to compare some physical and chemical properties Naon 117. 3.2. SW measurements Fig. 2 shows the swelling feature of the membranes (Naon 117, 5N-DDS and 5N-sDDS) in different methanol solutions, respectively. As shown in Fig. 2, when the concen-

tration of methanol solution increases, the Naon 117 membrane swells greatly and the uptake is up to 47%. Yet those composite membranes swell much smaller than Naon 117 membrane in the high methanol concentration solutions, for example, an increase of 30% of the 5N-sDDS membrane was tested in 3 M solution while the increase of the Naon 117 is up to 39%. However, the 5N-DDS composite membrane swells smaller than the 5N-sDDS, partly due to the strong hydrophobic properties of the two unreacted phenyl groups. The EW measurement shows that the 5N-sDDS composite membrane has lower EW (EW = 1040) than Naon 117 while the proton conductivity is still smaller than the Naon 117, which is similar to the zirconium phosphate/Naon composite membranes [23]. Since the proton conductivity of Naon is closely related with the content of water and the majority of the composites are still Naon resin [24], one can also expect a smaller proton conductivity of the composite membranes compared with commercial Naon membrane from the results of SW test. 3.3. FT-IR and SEM characterization Figs. 3 and 4 shows the FTIR spectra of sulfonated sDDS and N-sDDS composite membrane. The bands at 1595 cm1 ((C C)), 1432 cm1 ((CH2 )), 739 cm1 (( CH)), 698 cm1 ( (ring)) are attributed to characteristic vibrations of the benzene group. The band at 3414 cm1 is ascribed to a hydrated sulfonic group. The band at 1034 cm1 is assigned to the symmetric stretching of a sulfonic group [16]. The band at 922 cm1 is ascribed to terminal SiOH groups. The band at 1133 cm1 is assigned to Si O Si asymmetric stretching. The DDS silica structure (with sulfonated phenyl groups) was clearly veried. The peaks at 1204, 1129, 1052, 980 and 969 cm1 are ascribed to characteristic functional groups in Naon [20]. Additional peaks at 1593, 1429 cm1 are observed in the spectrum of N-sDDS, and they are attributed to phenyl groups of sDDS. It is clear

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C. Li et al. / Journal of Membrane Science 272 (2006) 5057

Fig. 6. Performances of DMFC with different membranes. Methanol concentration and ow rate: 1.0 M and 1.0 ml min1 . Oxygen pressure: 0.2 MPa, anode catalyst loading: PtRu/C, 2.0 mg cm2 , cathode catalyst loading: Pt/C 1.0 mg cm2 . Fig. 3. FT-IR spectra of sulfonated silane.

scope (SEM, Philips Cambridge S360). The membranes were freeze-fractured in liquid N2 for SEM observations. The representative cross-sectional images of the samples are shown in Fig. 5. From the SEM images, the silica particles can be clearly seen and the particulates are uniform tens of nanometers. Since the organosilica has the hydrophilic functional group, these particles should be embedded in the Naon matrix and due to the cage effects of the clusters of Naon; while the unsulfonated organosilica has low cage effect interaction with the clusters of Naon, therefore the particles are larger than sDDS. 3.4. Single cell performance Fig. 6 shows the performances of the Naon 117, 5NsDDS and 5N-DDS composite membranes at 75 C with the 1 M methanol respectively. The DMFC performance using Naon 117 membrane is the best of all because of its high proton conductivity and the pure Naon material used. An improved cell performance is also obtained using the sDDS composite membrane compared with the pure DDS membrane with the same 5% silica in weight, which suggests that the sulfonation of the DDS is useful. The slope of a IV curve reects the ohmic resistance of the fuel cell and

Fig. 4. FT-IR spectra of N-sDDS composite membrane.

that the sDDS was successfully introduced into Naon membrane. The microstructure of barely recast Naon membrane, 5N-sDDS composite membranes and 5N-DDS composite membranes were examined with a scanning electron micro-

Fig. 5. SEM images of barely recast Naon membrane (left), 5N-sDDS composite membrane (center) and 5N-DDS composite membrane (right).

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Fig. 7. Comparison of Naon 117 and 5N-sDDS composite membrane with 5 M methanol at 75 C. Methanol concentration and ow rate: 1.0 M, 5 M and 1.0 ml min1 . Oxygen pressure: 0.2 MPa.

Fig. 8. Methanol permeability as the function of the sDDS content.

one can notice the ohmic resistance of the 5N-sDDS and Naon 117 is almost the same. This is coinciding with the results gotten from the AC impedance mentioned above. Generally, the single cell performance of the DMFC using Naon 117 with the 1 M methanol is better than with the 5 M methanol, yet the tendency is not evident when using 5N-sDDS composite membrane. One can see a comparable performance with the 5 M methanol of 5N-sDDS and Naon 117 (Fig. 7). As for the Naon 117, the high concentration of methanol causes a decreasing of the open circuit voltage and the performance while for the composite membranes, it almost changed a little. The higher open circuit voltage of 5N-sDDS composite demonstrate a less methanol permeation. This phenomenon implies that the adulterated sDDS can have the function of reducing the methanol permeation and if optimized, such hybrid composite membranes can perform better performance than the native Naon when using high methanol concentration, which is useful in practice. 3.5. Methanol permeation measurements Fig. 8 shows the trend of the methanol permeation as a function of sDDS content at room temperature (25 C). The methanol concentration in the receiving compartment as a function of time is given by: VB dCB CA = ADK dt L (4)

the membrane is a constant and (2) K does not depend on the concentration. Therefore, the membrane permeability P (P = DK) could be simplied as: P= 1 CB (t) VB L A CA (t t0 ) (5)

Therefore, the permeability was calculated from the gradient of the straight lines obtained from plots of the data [25]. Evidently, the composite membranes reduced the methanol crossover compared with bare recast membrane and the reduction of methanol permeability varies with the amount of sDDS incorporated. The methanol permeability drops by a factor of 0.41, 0.61, 0.67, and 0.71 times for 5N-sDDS, 10NsDDS, 20N-sDDS and 25N-sDDS, respectively as compared to bare recast Naon. The 15N-sDDS composite membrane was broken with expectable reasons and therefore no relative data here. With the increasing of the amount of the hybrids, the methanol permeability decreased.

where CB and CA are the two methanol concentrations, A and L represent the membrane area and thickness, and D and K are the methanol diffusivity and partition coefcient between the membrane and adjacent solution, respectively. The following assumptions were made: (1) D inside the membrane is the constant and (2) K does not depend on the concentration. The following assumptions were made: (1) D inside

Fig. 9. Methanol permeability of membranes at different temperature.

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C. Li et al. / Journal of Membrane Science 272 (2006) 5057 concentration methanol fuel in DMFC, Electrochem. Commun. 5 (2003) 571. Z.Q. Ma, P. Cheng, T.S. Zhao, A palladium-alloy deposited Naon membrane for direct methanol fuel cells, J. Membr. Sci. 215 (2003) 327. Z.G. Shao, X. Wang, I.M. Hsing, Composite Naon/polyvinyl alcohol membranes for the direct methanol fuel cell, J. Membr. Sci. 210 (2002) 147. M.A. Smit, A.L. Ocampo, M.A. Espinosa-Medina, P.J. Sebastian, A modied Naon membrane with in situ polymerized polypyrrole for the direct methanol fuel cell, J. Power Sources 124 (2003) 59. V. Tricoli, F. Nannetti, ZeoliteNaon composites as ion conducting membrane materials, Electrochim. Acta 48 (2003) 2625. P. Dimitrova, K.A. Friedrich, U. Stimming, B. Vogt, Modied Naon -based membranes for use in direct methanol fuel cells, Solid State Ionics 150 (2002) 115. D.H. Jung, S.Y. Cho, D.H. Peck, D.R. Shin, J.S. Kim, Preparation and performance of a Naon /montmorillonite nanocomposite membrane for direct methanol fuel cell, J. Power Sources 118 (2003) 205. J. Liu, H. Wang, S. Cheng, K. Yuhan, Naon-polyfurfuryl alcohol nanocomposite membranes with low methanol permeation, Chem. Commun. (2004) 728. M. Watanabe, H. Uchida, Y. Seki, M. Emori, P. Stonehart, Selfhumidifying polymer electrolyte membranes for fuel cells, J. Electrochem. Soc. 143 (1996) 3847. M. Watanabe, H. Uchida, M. Emori, Polymer electrolyte membranes incorporated with nanometer-size particles of Pt and/or metaloxides: experimental analysis of the self-humidication and suppression of gas-crossover in fuel cells, J. Phys. Chem. B 102 (1998) 3129. B. Tazi, O. Savadogo, Effect of various heteropolyacids (HPAs) on the characteristics of Naon -HPAS membranes and their H-2/O-2 polymer electrolyte fuel cell parameters, J. New Mater., Electrochem. Syst. 4 (2001) 187. B. Tazi, O. Savadogo, Parameters of PEM fuel-cells based on new membranes fabricated from Naon , silicotungstic acid and thiophene, Electrochim. Acta 45 (2000) 4329. P.L. Antonucci, A.S. Arico, P. Creti, E. Ramunni, V. Antonucci, Solid State Ionics 125 (1999) 431; A.S. Arico, V. Antonucci, European Patent, EP 0926754A1 (1999). H.T. Wang, A. Brett, L.M. Holmberg, Z. Huang, B. Wang, A. Mitra, J.M. Norbeck, Y.S. Yan, Naonbifunctional silica composite proton conductive membranes, J. Mater. Chem. 12 (2002) 834. Z. Wei, S. Wang, B. Yi, G. Liu, L. Chen, W. Zhou, W. Li, Q. Xin, Inuence of electrode structure on the performance of a direct methanol fuel cell, J. Power Sources 106 (2002) 364. N. Carretta, V. Tricoli, F. Picchioni, Ionomeric membranes based on partially sulfonated poly(strene): synthesis, proton conduction and methanol permeation, J. Membr. Sci. 166 (2000) 189. X. Ren, T.E. Springer, T.A. Zawodzinski, S. Gottesfeld, Methanol transport through Naon membranes electro-osmotic drag effects on potential step measurements, J. Electrochem. Soc. 147 (2) (2000) 466. G. Luneau, A. Denoyelle, J.Y. Sanchez, C. Poinsignon, Organicinorganic protonic polymer electrolytes as membrane for low-temperature fuel cell. I, Electrochem. Acta 37 (1992) 1615. B. Libby, Improving selectivity in methanol fuel cell membranes: a study of a polymerzeolite composite membrane, Ph.D. Dissertation, University of Minnesota, 2001, pp. 5570. F. Damay, L.C. Klein, Transport properties of Naon composite membranes for proton-exchange membranes fuel cells, Solid State Ionics 162163 (2003) 261.

Fig. 9 shows the limiting methanol permeation current density as a function of temperature for the membranes. In Fig. 9, 1 M methanol solution was fed into the anode. The methanol permeation increased with the increasing of the temperature. Since the ohmic resistance is almost the same for the 125 m 5N-sDDS composite membrane and Naon 117, the limiting current density reects the methanol permeation of the two membranes. As can be seen from the graph, the methanol permeability of the Naon 117 membranes is larger than that of 5N-sDDS composite membranes from 30 to 75 C. Since the bare recast membrane are pure Naon material as the Naon 117, these results agree well with the results we got from the gas chromatography.

[4]

[5]

[6]

[7] [8]

[9]

4. Conclusion Diphenyldimethoxysilane (DDS) monomer can be sulfonated and acted as the additive to Naon solution to recast and form the N-sDDS composite membranes. The sDDS composite membrane performs better than the unreacted DDS/Naon composite when using the same amount of silica. And the SW tests also show the sulfonation of the monomer has the positive function compare with the pure DDS monomer. FT-IR and SEM characterizations reveal the incorporation of the hybrids in the composite membranes. Though the proton conductivity of the composite membranes decreased, the methanol permeability also reduced, which is useful and important in DMFCs.
[10]

[11]

[12]

[13]

[14]

Acknowledgements The authors wish to thank the Innovation Foundation of Chinese Academy of Science (K2003D2), the National Natural Science Foundation of China (Grant No. 20173060), National Natural Science Foundation of China Hi-Tech Research and Development Program of China (2003AA517040) and Knowledge Innovation Program of the Chinese Academy of Sciences (KGCX2-SW-310) for nancial support. The authors would like to thank Hu Bei Huabang Chemical Co. Ltd. for supplying diphenyldimethoxysilane monomer.

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